Yin J.-J,
Wang Y.-P,
Xue J,
Zhou F.-F,
Shan X.-Q,
Zhu R,
Fang K,
Shi L,
*,
Zhang S.-Y,
Hou S.-H,
*,
Xia W,
Tu Y.-Q.
*
Harbin Institute of Technology, Shanghai Jiao Tong University and Lanzhou University, P. R. of China
Total Syntheses of Polycyclic Diterpenes Phomopsene, Methyl Phomopsenonate, and
iso-Phomopsene via Reorganization of C–C Single Bonds.
J. Am. Chem. Soc. 2023;
145: 21170-21175
DOI:
10.1021/jacs.3c07044
Key words
(±)-
iso-phomopsene - diterpenoid - Ghosez cycloaddition - Knoevenagel condensation - Nazarov cyclization - Wagner–Meerwein rearrangement - Krapcho decarboxylation - Rubottom oxidation - Beckmann fragmentation - carbonyl–ene cyclization - Dess–Martin oxidation - Kumada coupling
Significance
Shi, Hou, Tu and co-workers report the total synthesis of phomopsene, methyl phomopsenonate, and iso-phomopsene. These natural products feature a 5/5/6/5 tetracyclic skeleton. The authors revised the structure of iso-phomopsene in this work.
Comment
Key to success is an InCl3-catalyzed Nazarov cyclization of dicyclobutane K followed by Wagner–Meerwein rearrangements to afford tetracycle M. Ring expansion via Beckmann fragmentation completed the carbocyclic framework.
